JP2024540045A - Thermoplastic compositions, methods for making thermoplastic compositions, and articles including thermoplastic compositions - Patents.com - Google Patents

Abstract

The thermoplastic composition includes a poly(phenylene ether)-poly(siloxane) block copolymer reaction product in specified amounts, an impact modifier, an organophosphate ester flame retardant, and a second poly(phenylene ether). The composition may be useful in a variety of articles, particularly as a component of an electric vehicle battery.

Description

The present invention relates to a thermoplastic composition, a method for producing the thermoplastic composition, and an article comprising the thermoplastic composition.

CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to and the benefit of European Patent Application No. 21205340.9, filed October 28, 2021, the contents of which are incorporated herein by reference in their entirety.

Poly(arylene ethers) are commercially attractive materials due to their unique combination of properties including, for example, high temperature resistance, dimensional and hydrolytic stability, and electrical properties.

There is a continuing need in the art for poly(arylene ether) compositions that have low flammability, particularly for thin wall applications. In addition to low flammability, it would be further advantageous if the compositions also exhibited high heat resistance, high impact strength, and hydrolysis resistance.

The thermoplastic composition comprises 5 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a first poly(phenylene ether); 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; 5 to 20 weight percent of an organophosphate ester flame retardant; less than 3 weight percent of a reinforcing filler; less than 0.5 weight percent tricalcium phosphate; and 40 to 90 weight percent of a second poly(phenylene ether), the weight percent of each component being based on the total weight of the composition.

The method of making the composition includes melt mixing the components of the composition.

An article comprises the composition. For example, an electric vehicle battery component can be extruded from the composition, and preferably the electric vehicle battery component is an electric vehicle battery insulating sheet or film.

The above and other features are illustrated in the detailed description below.

The present inventors have unexpectedly discovered that certain thermoplastic compositions can provide a desirable combination of properties. More specifically, compositions comprising certain amounts of a poly(phenylene ether)-polysiloxane block copolymer reaction product, a second poly(phenylene ether), a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, and an organophosphate ester flame retardant can provide a desirable combination of low flammability, high heat resistance, high impact strength, and hydrolysis resistance.

Thus, one aspect of the present disclosure is a thermoplastic composition. The thermoplastic composition includes a poly(phenylene ether)-polysiloxane block copolymer reaction product including a first poly(phenylene ether) and a poly(phenylene ether)-poly(siloxane) block copolymer. As used herein, the term "poly(phenylene ether)-polysiloxane block copolymer" refers to a block copolymer including at least one poly(phenylene ether) block and at least one polysiloxane block.

The poly(phenylene ether) block of the poly(phenylene ether)-poly(siloxane) block copolymer has the formula (1):
(1)
wherein each occurrence of Z ¹ is independently halogen, unsubstituted or substituted C _1-12 hydrocarbyl, provided that the hydrocarbyl group is not tertiary hydrocarbyl, C _1-12 hydrocarbylthio, C _{1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy} and at least two carbon atoms separate the halogen and oxygen atoms; and each occurrence of Z ² is independently hydrogen, halogen, unsubstituted or substituted C _1-12 hydrocarbyl, provided that the hydrocarbyl group is not tertiary hydrocarbyl, C _1-12 hydrocarbylthio, C _1-12 hydrocarbyloxy, or C _2-12 halohydrocarbyloxy and at least two carbon atoms separate the halogen and oxygen atoms. As used herein, the term "hydrocarbyl," whether used by itself or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched-chain, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched-chain, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as being substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, particularly when described as being substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, and the like, or may contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z ¹ may be a di-n-butylaminomethyl group formed by reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

In one embodiment, the poly(phenylene ether) blocks comprise 2,6-dimethyl-1,4-phenylene ether repeating units, i.e., formula (2):
(2)
2,3,6-trimethyl-1,4-phenylene ether repeat units, or a combination thereof.

Poly(phenylene ether) may include molecules with aminoalkyl-containing end groups typically located ortho to the hydroxyl groups. Tetramethyldiphenoquinone (TMDQ) end groups are also often present, typically obtained from 2,6-dimethylphenol-containing reaction mixtures in which tetramethyldiphenoquinone by-product is present. Poly(phenylene ether) may be in the form of homopolymers, copolymers, graft copolymers, ionomers, or block copolymers, as well as combinations thereof.

The polysiloxane block is a residue of a hydroxyaryl-terminated polysiloxane. In one embodiment, the polysiloxane block is represented by formula (3):
(3)
wherein each occurrence of R ¹ and R ² is independently hydrogen, C _1-12 hydrocarbyl, or C _1-12 halohydrocarbyl; and the polysiloxane block comprises repeat units according to formula (4):
(4)
wherein Y is hydrogen, C _1-12 hydrocarbyl, C _1-12 hydrocarbyloxy, or halogen, and each occurrence of R ³ and R ⁴ is independently hydrogen, C _1-12 hydrocarbyl, or C _1-12 halohydrocarbyl. In one aspect, the polysiloxane repeat units include dimethylsiloxane (-Si(CH ₃ ) ₂ O-) units. In one aspect, the polysiloxane blocks include terminal units of formula (5):
(5)
wherein n is on average 20-60.

The hydroxyaryl-terminated polysiloxane comprises at least one hydroxyaryl end group. In one aspect, the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl end group, in which case a poly(phenylene ether)-polysiloxane diblock copolymer is formed. In one aspect, the hydroxyaryl-terminated polysiloxane has two hydroxyaryl end groups, in which case a poly(phenylene ether)-polysiloxane diblock copolymer and/or a poly(phenylene ether)-polysiloxane-poly(phenylene ether) triblock copolymer is formed. It is also possible for the hydroxyaryl-terminated polysiloxane to have three or more hydroxyaryl end groups and a branched structure that allows for the formation of the corresponding branched block copolymers.

In one embodiment, the hydroxyaryl-terminated polysiloxane contains, on average, 20 to 80 siloxane repeat units, specifically 25 to 70 siloxane repeat units, more specifically 30 to 60 siloxane repeat units, even more specifically 35 to 50 siloxane repeat units, and even more specifically 40 to 50 siloxane repeat units. The number of siloxane repeat units in the polysiloxane block is essentially unaffected by the copolymerization and isolation conditions and is therefore equal to the number of siloxane repeat units in the hydroxyaryl-terminated polysiloxane starting material. If not otherwise known, the average number of siloxane repeat units per hydroxyaryl-terminated polysiloxane molecule can be determined by nuclear magnetic resonance (NMR) techniques in which the intensity of the signal associated with the siloxane repeat unit is compared to the intensity of the signal associated with the hydroxyaryl end group. For example, if the hydroxyaryl-terminated polysiloxane is a polydimethylsiloxane capped with eugenol, the average number of siloxane repeat units can be determined by the proton nuclear magnetic resonance ( ¹ H NMR) method of comparing the integrals of the protons of the dimethylsiloxane resonance and the protons of the methoxy groups of eugenol.

In one embodiment, the poly(phenylene ether)-polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 grams per mole (g/mol). For example, the reaction product may have a weight average molecular weight of 30,000 to 150,000 g/mol, specifically 35,000 to 120,000 g/mol, more specifically 40,000 to 90,000 g/mol, and even more specifically 45,000 to 70,000 g/mol. In one embodiment, the poly(phenylene ether)-polysiloxane block copolymer reaction product has a number average molecular weight of 10,000 to 50,000 g/mol, specifically 10,000 to 30,000 g/mol, and more specifically 14,000 to 24,000 g/mol.

In one embodiment, the poly(phenylene ether)-polysiloxane block copolymer reaction product has an intrinsic viscosity of at least 0.3 deciliters per gram as measured by Ubbelohde viscometer in chloroform at 25° C. In one embodiment, the intrinsic viscosity is 0.3 to 0.5 deciliters per gram, specifically 0.31 to 0.5 deciliters per gram, and more specifically 0.35 to 0.47 deciliters per gram.

The poly(phenylene ether)-polysiloxane block copolymer is prepared by an oxidative copolymerization method. In this method, the poly(phenylene ether)-polysiloxane block copolymer is the product of a process that includes oxidative copolymerization of a monomer mixture that includes a monohydric phenol and a hydroxyaryl-terminated polysiloxane. In one aspect, the monomer mixture includes 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. The hydroxyaryl-diterminated polysiloxane and the monohydric phenol can be as described above.

The oxidative copolymerization process produces poly(phenylene ether)-polysiloxane block copolymers as the desired product and poly(phenylene ether) (without incorporated polysiloxane blocks) as a by-product. Separation of the poly(phenylene ether) from the poly(phenylene ether)-polysiloxane block copolymer is not necessary. Thus, the poly(phenylene ether)-polysiloxane block copolymer is available as a "reaction product" containing both poly(phenylene ether) and poly(phenylene ether)-polysiloxane block copolymer. Specific separation procedures, such as precipitation from isopropanol, can be used to ensure that the reaction product is essentially free of residual hydroxyaryl-terminated polysiloxane starting material. In other words, these separation procedures ensure that the polysiloxane content of the reaction product is essentially all in the form of poly(phenylene ether)-polysiloxane block copolymer. Detailed methods for forming poly(phenylene ether)-polysiloxane block copolymers are described in U.S. Pat. Nos. 8,017,697 and 8,669,332 to Carrillo et al.

The poly(phenylene ether)-polysiloxane block copolymer reaction product may contain 1 to 30 weight percent siloxane repeat units and 70 to about 99 weight percent phenylene ether repeat units, based on the total weight of the reaction product. It will be understood that the siloxane repeat units are derived from a hydroxyaryl-terminated polysiloxane and the phenylene ether repeat units are derived from a monohydric phenol. In one aspect, for example, when the poly(phenylene ether)-polysiloxane block copolymer reaction product is purified by precipitation in isopropanol, the siloxane repeat units consist essentially of residues of hydroxyaryl-terminated polysiloxanes incorporated into the poly(phenylene ether)-polysiloxane block copolymer.

In one aspect, the poly(phenylene ether)-polysiloxane block copolymer comprises phenylene ether repeat units derived from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and combinations thereof. In one aspect, the poly(phenylene ether)-polysiloxane block copolymer may, for example, comprise 0.05 to 2 weight percent, specifically 0.1 to 1 weight percent, and more specifically 0.2 to 0.8 weight percent of siloxane groups relative to the total composition.

The composition includes the poly(phenylene ether)-polysiloxane block copolymer reaction product in an amount of 5 to 40 weight percent, based on the total weight of the composition. Within this range, the poly(phenylene ether)-polysiloxane block copolymer reaction product may be present in an amount of at least 8 weight percent, or at least 10 weight percent, or at least 12 weight percent, or at least 15 weight percent, or at least 20 weight percent, or at least 22 weight percent, or at least 24 weight percent. Also within this range, the poly(phenylene ether)-polysiloxane block copolymer reaction product may be present in an amount of 35 weight percent or less, or 32 weight percent or less, or 30 weight percent or less, or 28 weight percent or less. In one aspect, the poly(phenylene ether)-polysiloxane block copolymer reaction product may be present in an amount of 8 to 40 weight percent, or 8 to 35 weight percent, or 8 to 30 weight percent, or 8 to 28 weight percent, or 10 to 28 weight percent.

In addition to the poly(phenylene ether)-polysiloxane block copolymer reaction product, the thermoplastic composition further comprises a second poly(phenylene ether).

The second poly(phenylene ether) may have an intrinsic viscosity of greater than 0.25 deciliters per gram, preferably 0.44 to 0.60 deciliters per gram, and more preferably 0.44 to 0.50 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer. In one aspect, the second poly(phenylene ether) comprises homopolymers or copolymers of the monomers 2,6-dimethylphenol, 2,3,6-trimethylphenol, and combinations thereof.

In one aspect, the second poly(phenylene ether) may have an intrinsic viscosity greater than 0.43 deciliters per gram, and preferably, the second poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether).

The composition may include a second poly(phenylene ether) in an amount of 40 to 89 weight percent, based on the total weight of the composition. Within this range, the amount of the second poly(phenylene ether) can be 45 to 89 weight percent, or 45 to 75 weight percent, or 50 to 75 weight percent, or 50 to 70 weight percent, or 50 to 60 weight percent.

In one embodiment, the composition may comprise a poly(phenylene ether)-poly(siloxane) block copolymer reaction product and a second poly(phenylene ether) in a combined amount of at least 70 weight percent, or from 70 to 94 weight percent, or from 75 to 85 weight percent, based on the total weight of the composition.

The composition further comprises a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene. For brevity, this component is referred to as the "hydrogenated block copolymer." The hydrogenated block copolymer may comprise 10 to 90 weight percent poly(alkenyl aromatic) content and 90 to 10 weight percent hydrogenated poly(conjugated diene) content, based on the weight of the hydrogenated block copolymer. In one aspect, the hydrogenated block copolymer is a low poly(alkenyl aromatic content) hydrogenated block copolymer having a poly(alkenyl aromatic) content of less than 10 to 40 weight percent, or 20 to 35 weight percent, or 25 to 35 weight percent, or 30 to 35 weight percent, all based on the weight of the low poly(alkenyl aromatic) content hydrogenated block copolymer. In one embodiment, the hydrogenated block copolymer is a high poly(alkenyl aromatic content) hydrogenated block copolymer having a poly(alkenyl aromatic content) content of 40 to 90 weight percent, or 50 to 80 weight percent, or 60 to 70 weight percent, all based on the weight of the high poly(alkenyl aromatic content) hydrogenated block copolymer.

In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 g/mol. Number average molecular weight and weight average molecular weight can be determined by gel permeation chromatography based on comparison to polystyrene standards. In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 g/mol, or 220,000 to 350,000 g/mol. In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 200,000 g/mol, or 40,000 to 180,000 g/mol, or 40,000 to 150,000 g/mol.

The alkenyl aromatic monomer used to prepare the hydrogenated block copolymer is represented by the formula (6):
(6)
wherein R ⁵ and R ⁶ each independently represent a hydrogen atom, a C _1-8 alkyl group, or a C _2-8 alkenyl group, R ⁷ and R ¹¹ each independently represent a hydrogen atom, a C _1-8 alkyl group, a chlorine atom, or a bromine atom, and R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom, a C _1-8 alkyl group, or a C _2-8 alkenyl group, or R ⁸ and R ¹⁰ together with the central aromatic ring form a naphthyl group, or R ⁹ and R ¹⁰ together with the central aromatic ring form a naphthyl group. Specific alkenyl aromatic monomers include, for example, styrene, chlorostyrenes, such as p-chlorostyrene, methylstyrenes, such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrenes, such as 3-t-butylstyrene and 4-t-butylstyrene. In one embodiment, the alkenyl aromatic monomer is styrene.

The conjugated diene used to prepare the hydrogenated block copolymer can be a C _4-20 conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like, and combinations thereof. In one aspect, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or combinations thereof. In one aspect, the conjugated diene is 1,3-butadiene.

A hydrogenated block copolymer is a copolymer comprising at least one block (A) derived from an alkenyl aromatic compound and at least one block (B) derived from a conjugated diene, in which the content of aliphatic unsaturated groups in block (B) is at least partially reduced by hydrogenation. In one embodiment, the aliphatic unsaturation in block (B) is reduced by at least 50 percent, or at least 70 percent. The arrangement of blocks (A) and (B) includes linear structures, graft structures, and radial teleblock structures with or without branching. Linear block copolymers include tapered linear structures and non-tapered linear structures. In one embodiment, the hydrogenated block copolymer has a tapered linear structure. In one embodiment, the hydrogenated block copolymer has a non-tapered linear structure. In one embodiment, the hydrogenated block copolymer comprises a (B) block comprising random incorporation of an alkenyl aromatic monomer. The structure of the linear block copolymer includes diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures, as well as linear structures containing a total of six or more blocks (A) and (B), where the molecular weight of each (A) block may be the same as or different from the molecular weight of the other (A) blocks, and the molecular weight of each (B) block may be the same as or different from the molecular weight of the other (B) blocks. In one embodiment, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

In one embodiment, the hydrogenated block copolymer does not contain residues of monomers other than alkenyl aromatic compounds and conjugated dienes. In one embodiment, the hydrogenated block copolymer is comprised of blocks derived from alkenyl aromatic compounds and conjugated dienes. The hydrogenated block copolymer does not contain grafts formed from these or other monomers. It also does not contain heteroatoms, since it is comprised of carbon and hydrogen atoms. In one embodiment, the hydrogenated block copolymer contains residues of one or more acid functionalizing agents, such as maleic anhydride. In one embodiment, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

In one embodiment, the hydrogenated block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a polystyrene content of 10 to 50 weight percent, or 20 to 40 weight percent, or 20 to 35 weight percent, or 25 to 35 weight percent, based on the weight of the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. In these embodiments, the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer can optionally have a weight average molecular weight of 200,000 to 400,000 grams/mole, or 250,000 to 350,000 grams/mole, as determined by size exclusion chromatography using polystyrene standards.

Methods for preparing hydrogenated block copolymers are known in the art, and many hydrogenated block copolymers are commercially available. Exemplary commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as Kraton™ G1701 (having 37 weight percent polystyrene) and G1702 (having 28 weight percent polystyrene); and polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as Kraton™ G1641 (having 33 weight percent polystyrene), G1650 (having 30 weight percent polystyrene), G1651 (having 33 weight percent polystyrene), and G1654 (having 31 weight percent polystyrene). and polystyrene-poly(ethylene-ethylene/propylene)-polystyrene triblock copolymers available from Kuraray Co., Ltd. as SEPTON™ S4044, S4055, S4077, and S4099. Additional commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-ethylene/propylene)-polystyrene triblock copolymers available from Dynasol as CALPRENE™ H6140 (having 31 weight percent polystyrene), H6170 (having 33 weight percent polystyrene), H6171 (having 33 weight percent polystyrene) and H6174 (having 33 weight percent polystyrene), and polystyrene-poly(ethylene-propylene)-polystyrene triblock copolymers available from Kuraray Co., Ltd. as SEPTON™ 8006 (having 33 weight percent polystyrene) and 8007 (having 30 weight percent polystyrene). polystyrene-poly(ethylene-propylene)-polystyrene (SEBS) triblock copolymers available from Kuraray Co., Ltd. as SEPTON™ 2006 (having 35 weight percent polystyrene) and 2007 (having 30 weight percent polystyrene); oil-extended compounds of these hydrogenated block copolymers available from Kraton Performance Polymers Inc. as Kraton™ G4609 (containing 45% mineral oil, and SEBS with 33 weight percent polystyrene) and G4610 (containing 31% mineral oil, and SEBS with 33 weight percent polystyrene) and from Asahi Kasei Co., Ltd. as TUFTEC™ H1272 (containing 36% oil, and SEBS with 35 weight percent polystyrene). Mixtures of two or more hydrogenated block copolymers can be used. In one embodiment, the hydrogenated block copolymer comprises a polystyrene poly(ethylene-butylene)-polystyrene triblock copolymer having a weight average molecular weight of at least 100,000 grams/mole, or from 200,000 to 400,000 grams/mole.

The composition includes the hydrogenated block copolymer in an amount of 1 to 15 weight percent based on the total weight of the composition. Within this range, the amount of hydrogenated block copolymer can be 1 to 10 weight percent, or 3 to 8 weight percent, or 5 to 10 weight percent, or 4 to 8 weight percent, or 5 to 7 weight percent.

In one aspect, the composition may optionally further comprise homopolystyrene or high impact polystyrene. As used herein, the term homopolystyrene refers to a homopolymer of styrene. Thus, residues of any monomer other than styrene are excluded from homopolystyrene. Homopolystyrene may be atactic, syndiotactic, or isotactic. In one aspect, homopolystyrene may be atactic homopolystyrene. In one aspect, homopolystyrene may have a melt volume flow rate of 1.5 to 5 cubic centimeters per 10 minutes measured at 200° C. and 5 kilograms load according to ISO 1133. High impact polystyrene, also known as HIPS or rubber modified polystyrene, may comprise 80 to 96 weight percent polystyrene, specifically 88 to 94 weight percent polystyrene, and 4 to 20 weight percent polybutadiene, specifically 6 to 12 weight percent polybutadiene, based on the weight of the rubber modified polystyrene. In one embodiment, the rubber-modified polystyrene has an effective gel content of 10 to 35 percent.

When present, homopolystyrene or high impact polystyrene may be present in an amount of 0 to greater than 15 weight percent, or 1 to 10 weight percent, based on the total weight of the composition. In one aspect, homopolystyrene or high impact polystyrene may be excluded from the composition.

The composition further includes an organophosphate flame retardant. Exemplary organophosphate compounds include phosphate esters containing phenyl groups, substituted phenyl groups, or combinations of phenyl and substituted phenyl groups, bisaryl phosphate esters based on resorcinol, such as resorcinol bis(diphenyl phosphate), and bisaryl phosphate esters based on bisphenols, such as bisphenol A bis(diphenyl phosphate). In one aspect, the organophosphate ester is selected from the group consisting of tris(alkylphenyl)phosphate (e.g., CAS Reg. No. 89492-23-9 or CAS Reg. No. 78-33-1), resorcinol bis(diphenyl phosphate) (CAS Reg. No. 57583-54-7), bisphenol A bis(diphenyl phosphate) (CAS Reg. No. 181028-79-5), triphenyl phosphate (CAS Reg. No. 115-86-6), tris(isopropylphenyl)phosphate (e.g., CAS Reg. No. 68937-41-7), t-butylphenyl diphenyl phosphate (CAS Reg. No. 56803-37-3), bis(t-butylphenyl)phenyl phosphate (CAS Reg. No. 56803-37-3), bis(t-butylphenyl)phenyl phosphate (CAS Reg. No. 56803-37-4), bis(t-butylphenyl)phenyl phosphate (CAS Reg. No. 56803-37-5), bis(t-butylphenyl)phenyl phosphate (CAS Reg. No. 56803-37-6 ... Reg. No. 65652-41-7), tris(t-butylphenyl)phosphate (CAS Reg. No. 78-33-1), and combinations thereof.

In one embodiment, the organophosphate ester is represented by formula (7):
(7)
wherein R is, independently in each occurrence, a C _1-12 alkylene group; R ¹⁶ and R ¹⁷ are, independently in each occurrence, a C _1-5 alkyl group; R ¹² , R ¹³ , and R ¹⁵ are, independently, a C _1-12 hydrocarbyl group; R ¹⁴ is, independently in each occurrence, a C _1-12 hydrocarbyl group; n is 1 to 25; and s1 and s2 are independently integers equal to 0, 1, or 2. In one embodiment, OR ¹² , OR ¹³ , OR ¹⁴ , and OR ¹⁵ are independently derived from phenol, a monoalkylphenol, a dialkylphenol, or a trialkylphenol.

As will be readily understood by those skilled in the art, the bisarylphosphates are derived from bisphenols. Exemplary bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, and 1,1-bis(4-hydroxyphenyl)ethane. In one aspect, the bisphenol includes bisphenol A.

In one embodiment, the organophosphate ester includes resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, or a combination thereof.

The organophosphate ester may be present in the composition in an amount of 5 to 20 weight percent, based on the total weight of the composition. Within this range, the organophosphate ester may be present in an amount of 7 to 15 weight percent, or 8 to 14 weight percent, or 8.5 to 12.5 weight percent.

The thermoplastic composition may further optionally include an additive composition. The additive composition includes one or more additives. The additives may be, for example, stabilizers, release agents, lubricants, processing aids, drip retardants, nucleating agents, UV blocking agents, dyes, pigments, antioxidants, antistatic agents, foaming agents, mineral oils, metal deactivators, antiblocking agents, or combinations thereof. In one aspect, the additive composition may include antioxidants, lubricants, heat stabilizers, UV absorbing additives, plasticizers, anti-drip agents, release agents, antistatic agents, dyes, pigments, laser marking additives, radiation stabilizers, or combinations thereof. When present, such additives are typically used in a total amount of 0.1 to 10 weight percent based on the total weight of the composition.

In one aspect, the composition may include an anti-drip agent. Fluorinated polyolefins or polytetrafluoroethylene may be used as the anti-drip agent. Anti-drip agents, such as fibril-forming or non-fibril-forming fluoropolymers, such as polytetrafluoroethylene (PTFE), may also be used. The anti-drip agent may be encapsulated by a rigid copolymer, such as styrene acrylonitrile (SAN). PTFE encapsulated with SAN is known as TSAN. Encapsulated fluoropolymers may be made, for example, by polymerizing the encapsulating polymer in the presence of the fluoropolymer in an aqueous dispersion. TSAN may offer a significant advantage over PTFE in that it can be more easily dispersed in the composition. A suitable TSAN may, for example, include 50% PTFE and 50% SAN by weight, based on the total weight of the encapsulated fluoropolymer. SAN may, for example, include 75% styrene and 25% acrylonitrile by weight, based on the total weight of the copolymer. Alternatively, the fluoropolymer can be pre-blended in some manner with a second polymer, such as an aromatic polycarbonate resin or SAN, to form a granulation for use as an anti-drip agent. Either method can be used to make an encapsulated fluoropolymer.

The anti-drip agent can be added in the form of relatively large particles having a number average particle size of 0.3 to 0.7 mm, specifically 0.4 to 0.6 millimeters. The anti-drip agent can be used in an amount of 0.01% to 5.0% by weight, based on the total weight of the composition.

The composition may include less than 3 weight percent, or less than 1 weight percent, or less than 0.5 weight percent of reinforcing fillers. In one aspect, reinforcing fillers can be excluded from the composition. Reinforcing fillers include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripolites, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, borosilicate powder, calcium sulfate, calcium carbonate (e.g., chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, acicular, and flaky talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates or (armospheres), kaolin, silicon carbide, alumina, boron carbide, iron, nickel, or copper whiskers, continuous and chopped carbon or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO ₂ , aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground nut shells, or rice grain hulls, reinforcing organic fibrous fillers such as poly(ether ketones), polyimides, polybenzoxazoles, poly(phenylene sulfide), polyesters, polyethylenes, aromatic polyamides, aromatic polyimides, polyetherimides, polytetrafluoroethylene, and poly(vinyl alcohol), and combinations thereof. The fillers and reinforcing agents may be coated with a layer of metallic material to enhance electrical conductivity or surface treated with silanes to improve adhesion and dispersion in the polymer matrix. In one aspect, the composition may contain less than 5 percent by weight of glass fibers. In one aspect, the composition may be free of glass fibers.

The composition may include less than 0.5 weight percent, or less than 0.1 weight percent, or less than 0.01 weight percent tricalcium phosphate. In one aspect, the composition may be free of tricalcium phosphate. Tricalcium phosphate (CAS Reg. No. 1306-06-5) has the chemical formula Ca ₅ (OH) (PO ₄ ) ₃ and is also known as hydroxyapatite, hydroxylapatite, tricalcium phosphate, pentacalcium hydroxyorthophosphate, and apatite.

The composition may optionally minimize or eliminate additional ingredients not specifically described herein. For example, the composition may include less than 2 weight percent, or less than 1 weight percent, or less than 0.5 weight percent, or less than 0.1 weight percent of any thermoplastic polymer other than the poly(phenylene ether)-poly(siloxane) block copolymer reaction product, the second poly(phenylene ether), the hydrogenated block copolymer, polystyrene, and high impact polystyrene. In one aspect, the composition may exclude any thermoplastic polymer other than the aforementioned polymers of the composition. In one aspect, the composition may include minimal or no glass fibers. In one aspect, the composition may include minimal or no homopolystyrene or rubber modified polystyrene.

In one aspect, the composition may include 8 to 28 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product; 50 to 75 weight percent of a second poly(phenylene ether); 3 to 10 weight percent of a hydrogenated block copolymer; and 7 to 15 weight percent of an organophosphate ester flame retardant. The composition may be free of tricalcium phosphate and reinforcing fillers.

In one aspect, the composition may comprise a poly(phenylene ether)-polysiloxane block copolymer reaction product comprising a phenylene ether block comprising repeating units derived from 2,6-dimethylphenol and a siloxane block comprising repeating units derived from dimethylsiloxane; a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; an organophosphate flame retardant comprising resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, or a combination thereof, and a second poly(phenylene ether) comprising repeating units derived from 2,6-dimethylphenol. In one aspect, the composition may comprise 8 to 28 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product, 50 to 75 weight percent of the second poly(phenylene ether), 3 to 10 weight percent of the hydrogenated block copolymer, 7 to 15 weight percent of the organophosphate flame retardant comprising resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, or a combination thereof.

The compositions of the present disclosure may comprise 5 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a first poly(phenylene ether); 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; 5 to 20 weight percent of an organophosphate ester flame retardant; less than 3 weight percent of a reinforcing filler; less than 0.5 weight percent of tricalcium phosphate; and 40 to 89 weight percent, preferably 45 to 85 weight percent, of a second poly(phenylene ether), the weight percent of each component being based on the total weight of the composition. The poly(phenylene ether)-poly(siloxane) block copolymer reaction product and the second poly(phenylene ether) may be present in a combined amount of at least 70 weight percent, or 70 to 94 weight percent, or 75 to 85 weight percent, based on the total weight of the composition. The first poly(phenylene ether) may have an intrinsic viscosity of greater than 0.25 deciliters per gram, or from 0.4 to 0.6 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer, and preferably the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether). The organophosphate flame retardant may comprise resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, resorcinol bis(di 2,6-dimethylphenyl) phosphate, oligomeric phosphate esters, triphenyl phosphate, or combinations thereof, preferably bis-phenol A bis-diphenyl phosphate. The hydrogenated block copolymer may comprise polystyrene-poly(ethylene-butylene)-polystyrene. The composition may comprise 0 to 15 weight percent homopolystyrene or high impact polystyrene. The composition may further comprise 0.1 to 10 weight percent of the additive composition. The composition may be free of glass fibers. The composition may include 8 to 28 weight percent of a poly(phenylene ether)-polysiloxane block copolymer reaction product; 50 to 75 weight percent of a second poly(phenylene ether); 3 to 10 weight percent of a hydrogenated block copolymer; and 7 to 15 weight percent of an organophosphate flame retardant. The relative amounts of each component can be adjusted within the above ranges to obtain the desired combination of properties. As will be appreciated by one of ordinary skill in the art, the amounts of each component are selected such that their sum equals 100 weight percent.

The compositions of the present disclosure can exhibit a combination of desirable physical properties. For example, molded samples of the composition may exhibit a UL-94 flammability rating of V0 when measured using a 1.0 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C.; and a UL-94 flammability rating of V0 when measured using a 0.75 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C.; a UL-94 flammability rating of V0 when measured using a 0.5 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C.; a UL-94 flammability rating of V0 when measured using a 0.3 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C.; and a UL-94 flammability rating of V0 when measured using a 0.2 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C. Molded samples of the composition may exhibit a heat deflection temperature of 115° C. or greater, as measured on 3.2 mm thick strips using a load of 1.82 MPa according to ASTM D648. Molded samples of the composition may exhibit a notched Izod impact strength of 240 J/m or greater, as measured according to ASTM D256.

The compositions of the present disclosure can be prepared, for example, by melt blending the components of the composition. The components of the composition can be mixed or blended using conventional equipment, such as ribbon blenders, HENSCHEL™ mixers, BANBURY™ mixers, drum tumblers, and the like, and the blended composition can then be melt blended or melt kneaded. The melt blending or melt kneading can be carried out using conventional equipment, such as single screw extruders, twin screw extruders, multi-screw extruders, co-kneaders, and the like. For example, the compositions of the present disclosure can be prepared by melt blending the components in a twin screw extruder at a temperature of 270-310°C, or 280-300°C. The extrudate is immediately quenched in a water bath and pelletized. The pellets thus prepared can be ¼ inch or less in length, if desired. Such pellets can be used for subsequent molding, shaping, or forming.

Shaped, molded, or molded articles comprising the composition represent another aspect of the present disclosure. The composition can be molded into useful shaped articles by a variety of methods, including injection molding, extrusion, rotational molding, blow molding, and thermoforming. Some examples of articles include electric vehicle battery modules, battery housings, battery cases, battery cell frames, battery cell spacers, battery cell retainers, battery pack insulating films, bus bar holders, terminal covers, electrical or electronic components, thermoset circuit breakers, fuser holders for electrophotographic copiers, photovoltaic junction boxes, photovoltaic connectors, electrical connectors, automotive electrical connectors, relays, charging couplers, appliance components, automotive components, portable devices, mobile components, or stationary electrical components. In one embodiment, the article is an extrusion, a molded, a pultruded, a thermoformed, a foamed, a layer in a multilayer article, a substrate in a coated article, or a substrate in a metallized article. In one embodiment, the composition may be particularly useful in molded or extruded parts for electric vehicle battery components. For example, the composition may be used in extruded parts for electric vehicle battery components, such as insulating sheets or films for electric vehicle battery components.

A battery insulation film or sheet represents another aspect of the present disclosure. The battery insulation film or sheet is extruded from a composition comprising 5 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a first poly(phenylene ether); 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; 5 to 20 weight percent of an organophosphate ester flame retardant; less than 3 weight percent of a reinforcing filler; less than 0.5 weight percent of tricalcium phosphate; and 40 to 89 weight percent of a second poly(phenylene ether), the weight percent of each component being based on the total weight of the composition. In one embodiment, the extruded film or sheet has a UL-94 flammability rating of V0 when measured using a 1.0 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C.; and a UL-94 flammability rating of V0 when measured using a 0.75 millimeter specimen after conditioning for 48 hours at 23° C. and 168 hours at 70° C. It may also have a UL-94 flammability rating of V0 when measured using a 0.5 millimeter specimen after conditioning at 23° C. for 48 hours and at 70° C. for 168 hours; and a UL-94 flammability rating of V0 when measured using a 0.3 millimeter specimen after conditioning at 23° C. for 48 hours and at 70° C. for 168 hours. The extruded film or sheet may exhibit a heat deflection temperature of 115° C. or greater when measured on a 3.2 mm thick specimen using a load of 1.82 MPa according to ASTM D648, and a notched Izod impact strength of 240 J/m or greater when measured according to ASTM D256. The battery insulation film may have a thickness of, for example, 50 to 1000 micrometers.

As described herein, the inventors have unexpectedly discovered that compositions comprising specific amounts of a poly(phenylene ether)-polysiloxane block copolymer, a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, an organophosphate ester flame retardant, and a second poly(phenylene ether) can provide certain advantageous properties, particularly for thin molded articles, including a combination of high heat resistance, high impact strength, and low flammability. Thus, the present disclosure provides significant improvements, particularly as it relates to battery pack insulating films or sheets extruded from the compositions.

The present disclosure is further illustrated by the following non-limiting examples.

The materials used in the following examples are shown in Table 1.

The compositions were compounded using a Toshiba TEM-37BS twin screw extruder. All ingredients were added at the feed throat of the extruded except for BPADP, which was added via a liquid feeder. The extrudate was cooled in a water bath and pelletized. The pellets were conditioned at 120°C for 3 hours prior to injection molding or extrusion. The processing parameters used are summarized in Table 2.

Test pieces were injection molded on a Toshiba UH1000-110 injection molding machine operating at barrel temperatures of 290°C, 300°C, 300°C, and 290°C (feed throat to nozzle) and a mold temperature of 90°C.

The properties of the molded products were tested according to the following criteria:

The melt flow rate values, expressed in g/10 min, were measured at a temperature of 300°C and a load of 5 kilograms according to ASTM D1238-10, procedure B. The heat deflection temperature (HDT), expressed in °C, was measured at 1.82 MPa or 0.45 MPa using a load bar of 3.2 millimeters thickness according to ASTM D648. The notched Izod impact (NII) strength values, expressed in joules/meter, were measured at 23°C using a pendulum of cross-sectional dimensions of 3.2 millimeters by 12.7 millimeters according to ASTM D256-10, method A. The unnotched Izod impact strength, expressed in joules/meter, was measured at 23°C using a pendulum of cross-sectional dimensions of 3.2 millimeters by 12.7 millimeters according to ASTM D4812. Tensile properties were measured according to ASTM D638 with a sample thickness of 3.2 millimeters and a test speed of 5 millimeters per minute.

Hydrolytic stability was evaluated by placing tensile bars in a hydrolysis chamber at 85°C and 85% relative humidity for 1000 hours. Samples were then removed from the chamber for characterization. Hydrolytic stability was evaluated by retention of tensile modulus and tensile stress. Tensile modulus and tensile stress retention of 90% or greater was considered "good." Hydrolytic stability was considered "poor" if at least one of tensile modulus or tensile stress retention was less than 90%.

Density, expressed in grams per cubic centimeter (g/cc), was measured according to ASTM D-792 or ISO 1183-1, Method A.

Water absorption, expressed as percent weight change, was measured according to ASTM D-570 or ISO 62, Method 4.

The flame retardancy of the injection molded flame test specimens was measured according to Underwriter's Laboratory Bulletin 94 "Tests for Flammability of Plastic Materials, UL94", 20 mm vertical flame test. Flame test specimens of thickness 1.0, 0.75, 0.5, 0.3, and 0.2 millimeters were conditioned at 23°C and 50% relative humidity for at least 48 hours or at 70°C and 50% relative humidity for 168 hours before testing. Sets of 10 to 20 flame test specimens were tested for the UL94 20 mm vertical flame test. For each specimen, a flame was applied to the specimen for 10 seconds and then removed, and the time it took for the specimen to self-extinguish (time after first flame application t1) was recorded. The specimens were then again exposed to the flame for 10 seconds and removed, and the time it took for the specimens to self-extinguish (second flame time, t2) and glow red (afterglow time, t3) were recorded. To achieve a rating of V-0, the flame times t1 and t2 of each specimen must be 10 seconds or less, the total flame time for all five specimens (t1 + t2 for all five specimens) must be 50 seconds or less, the second flame time + afterglow time (t2 + t3) of each specimen must be 30 seconds or less, no specimen should burn or flare up to the position of the retaining clamp, and the cotton indicator should not be ignited by flame particles or drops. To achieve a V-1 rating, the post-flame times t1 and t2 of each individual specimen must be 30 seconds or less, the total post-flame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second post-flame time + afterglow time (t2 + t3) of each individual specimen must be 60 seconds or less, no specimen should burn or flare up to the position of the retaining clamps, and the cotton indicator should not be ignited by flame particles or droplets. To achieve a V-2 rating, the post-flame times t1 and t2 of each individual specimen must be 30 seconds or less, the total post-flame time for all five specimens (t1 + t2 for all five specimens) must be 250 seconds or less, the second post-flame time + afterglow time (t2 + t3) of each individual specimen must be 60 seconds or less, and no specimen may burn or blaze to the position of the retaining clamp, but the cotton indicator may be ignited by flame particles or droplets.

The composition and properties are summarized in Table 3. The amount of each component is provided as a weight percent based on the total weight of the composition.

As shown in Table 3, the composition of Comparative Example 1 exhibited flame retardancy of V0 at 0.75 mm, V2 at 0.5, 0.3 mm, and 0.2 mm. The composition of Comparative Example 2 exhibited improved HDT compared to Comparative Example 1, but exhibited reduced flammability, only achieving a V1 flammability rating at 0.75 mm. The composition of Comparative Example 3 exhibited improved flame retardancy with increased BPADP loading, but the HDT was reduced compared to Comparative Example 2. Thus, none of the comparative compositions achieve a V0 flammability rating at thicknesses below 0.75 mm, nor achieve a good balance between flame retardancy and heat resistance (e.g., HDT).

In contrast, the compositions of Examples 1-8 each exhibited a desirable combination of properties. Most notably, each of these compositions achieved a V0 flammability rating at thicknesses of 1.0, 0.75, 0.5, and 0.3 millimeters. The compositions of Examples 1-8, each containing PPE-Si, achieved a V0 flammability rating at a thickness of 0.3 millimeters, and the compositions of Examples 1-3 even achieved a V0 flammability rating at a thickness of 0.2 millimeters. In contrast, the compositions of Comparative Examples 1-3 achieved a V1 or V2 flammability rating at thicknesses of 0.5 millimeters or less. In addition to high flame retardancy, the compositions of Examples 1-8 also exhibited good hydrolysis resistance, heat resistance, and impact strength.

Thus, the compositions of the present disclosure can provide a V0 flammability rating at thicknesses of 0.3 mm or less, achieving a desirable balance of thin-wall flammability rating and high heat resistance.

The compositions of Examples 1 and 2 were further compared to various existing compositions. The results are summarized in Table 4. The composition of Comparative Example 4 is NORYL™ PX9406P, a non-brominated, non-chlorinated, flame retardant polyphenylene ether resin obtained from SABIC. The composition of Comparative Example 5 is FORMEX™ CND, a flame retardant polycarbonate obtained from ITW FORMEX. The composition of Comparative Example 6 is FORMEX™ GK, a flame retardant polypropylene obtained from ITW FORMEX.

These comparative examples were further evaluated for flammability according to UL94 VTM (Vertical Flammability Rating for Thin Materials). Samples were pretreated as described above. To achieve a rating of VTM-0, the flame time t1 and t2 of each individual specimen must be 10 seconds or less, the total flame time (t1+t2 of all five specimens) must be 50 seconds or less, the second flame time + afterglow time (t2+t3) of each individual specimen must be 30 seconds or less, no specimen should burn or flare up to the clamp position, and the cotton indicator should not be ignited by flame particles or drops. The thickness at which each composition achieves a rating of VTM-0 is presented in Table 4.

As shown in Table 4, existing compositions are unable to achieve the combination of flame retardancy, hydrolysis resistance and heat resistance for thin walls. Therefore, the compositions of the present disclosure provide a significant improvement.

The present disclosure further includes the following aspects:

Aspect 1: A thermoplastic composition comprising: 5 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a first poly(phenylene ether); 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; 5 to 20 weight percent of an organophosphate ester flame retardant; less than 3 weight percent of a reinforcing filler; less than 0.5 weight percent of tricalcium phosphate; and 40 to 90 weight percent of a second poly(phenylene ether), wherein the weight percent of each component is based on the total weight of the composition.

Aspect 2: The composition of aspect 1, wherein the second poly(phenylene ether) is present in an amount of 45 to 85 weight percent.

Aspect 3: The composition of aspect 1 or 2, wherein the poly(phenylene ether)-poly(siloxane) block copolymer reaction product and the second poly(phenylene ether) are present in a combined amount of at least 70 weight percent, or from 70 to 94 weight percent, or from 75 to 85 weight percent, based on the total weight of the composition.

Aspect 4: The composition according to any one of aspects 1 to 3, wherein a molded sample of the composition has a UL-94 flammability rating of V0 when measured using a 1.0 millimeter test specimen after conditioning for 48 hours at 23°C and for 168 hours at 70°C; a UL-94 flammability rating of V0 when measured using a 0.75 millimeter test specimen after conditioning for 48 hours at 23°C and for 168 hours at 70°C; A composition characterized by exhibiting either or both of: a UL-94 flammability rating of V0 when measured using a 0.5 millimeter test specimen after conditioning; a UL-94 flammability rating of V0 when measured using a 0.3 millimeter test specimen after conditioning for 48 hours at 23°C and for 168 hours at 70°C; a UL-94 flammability rating of V0 when measured using a 0.2 millimeter test specimen after conditioning for 48 hours at 23°C and for 168 hours at 70°C; and optionally a heat deflection temperature of 115°C or greater when measured using a 3.2 mm thick specimen using a load of 1.82 MPa according to ASTM D648; and a notched Izod impact strength of 240 J/m or greater when measured according to ASTM D256.

Aspect 5: The composition of any one of aspects 1 to 4, wherein the first poly(phenylene ether) has an intrinsic viscosity greater than 0.25 deciliters per gram, or from 0.4 to 0.6 deciliters per gram, as measured in chloroform at 25°C using an Ubbelohde viscometer, and preferably the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether).

Aspect 6: The composition of any one of aspects 1 to 5, wherein the organophosphate flame retardant comprises resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, resorcinol bis(di 2,6-dimethylphenyl) phosphate, oligomeric phosphate esters, triphenyl phosphate, or combinations thereof, preferably bis-phenol A bis-diphenyl phosphate.

Aspect 7: The composition according to any one of aspects 1 to 6, wherein the hydrogenated block copolymer comprises polystyrene-poly(ethylene-butylene)-polystyrene.

Aspect 8: The composition of any one of aspects 1 to 7, comprising 0 to 15 weight percent homopolystyrene or high impact polystyrene.

Aspect 9: A composition according to any one of aspects 1 to 8, characterized in that the composition does not contain glass fibers.

Aspect 10: The composition of any one of aspects 1 to 9, further comprising 0.1 to 10 weight percent of an additive composition.

Aspect 11: The composition of aspect 1, comprising: 8 to 28 weight percent of the poly(phenylene ether)-polysiloxane block copolymer reaction product; 50 to 75 weight percent of a second poly(phenylene ether); 3 to 10 weight percent of a hydrogenated block copolymer; and 7 to 15 weight percent of an organophosphate flame retardant.

Aspect 12: The composition of aspect 11, wherein the poly(phenylene ether)-polysiloxane block copolymer reaction product and the second poly(phenylene ether) are present in a combined amount of at least 75 weight percent, based on the total weight of the composition.

Aspect 13: A method for producing a composition according to any one or more of aspects 1 to 12, comprising melt mixing the components of the composition.

Aspect 14: An article comprising the composition of any one of aspects 1 to 12, preferably an electric vehicle battery module, a battery insulating sheet or film, a battery housing, a battery case, a battery cell frame, a battery cell spacer, a battery cell retainer, a bus bar holder, a terminal cover, an electric or electronic component, a charger adapter insulating sheet or film, a thermosetting circuit breaker, a fuser holder for an electrophotographic copier, a photovoltaic junction box, a photovoltaic connector, an electrical connector, an automotive electrical connector, a relay, a charging coupler, an appliance part, an automotive part, a portable device, a mobile part, or a stationary electrical part.

Aspect 15: An electric vehicle battery component extruded from the composition of any one of aspects 1 to 12, preferably an electric vehicle battery insulating sheet or film.

The compositions, methods, and articles can optionally include, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The compositions, methods, and articles can additionally or alternatively be formulated to be free or substantially free of any materials (or species), steps, or ingredients that are not necessary to accomplish the function or purpose of the compositions, methods, and articles.

All ranges disclosed herein are inclusive of endpoints, and the endpoints may be combined independently of one another. "Combinations" include blends, mixtures, alloys, reaction products, and the like. Terms such as "first," "second," and the like do not denote any order, quantity, or importance, but are used to distinguish one element from another. The terms "a," "an," and "the" do not denote any limitations of quantity, and should be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and/or" unless otherwise specified. References throughout this specification to "an embodiment" mean that the particular element described in connection with that embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. Any embodiment described herein can be combined with any other embodiment. As used herein, the term "combinations thereof" is open to include one or more of the listed elements and to allow for the presence of one or more similar elements not named. Further, it should be understood that the described elements may be combined in any suitable manner in the various embodiments.

Unless otherwise specified herein, all test standards are the latest standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application takes precedence over the conflicting term in the incorporated reference.

Compounds are described using standard nomenclature. For example, any position not substituted by any shown group is understood to have its valency satisfied by the shown bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

As used herein, the term "hydrocarbyl", whether used by itself or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as being substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituent residue. Thus, especially when described as being substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight-chain saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond, such as ethenyl (-HC=CH ₂ ). "Alkoxy" means an alkyl group attached through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight-chain or branched saturated divalent aliphatic hydrocarbon group, such as methylene (-CH ₂ -) or propylene (-(CH ₂ ) ₃ -). "Cycloalkylene" means a divalent cyclic alkylene group, -C _n H _2n-x , where x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds within the ring, all of the ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound that contains one or more of fluoro, chloro, bromo, or iodo substituents. Combinations of different halo atoms (e.g., bromo and fluoro) or only chloro atoms can be present. The prefix "hetero" refers to a compound or group that contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), each of which is independently N, O, S, Si, or P. "Substituted" means that a compound or group is substituted in place of a hydrogen with at least one (e.g., _{1, 2, 3, or 4) substituents which may each be independently C 1-9} alkoxy, C _1-9 haloalkoxy, nitro (-NO ₂ ), cyano (-CN), C _1-6 alkylsulfonyl (-S(=O) ₂ -alkyl), C 6-12 arylsulfonyl (-S(=O) ₂ -aryl), thiol (-SH), thiocyano (-SCN), tosyl ( _{CH 3} C _{6 H 4} SO ₂ -), C _3-12 cycloalkyl, C _2-12 alkenyl, C _5-12 cycloalkenyl, C _{6-12 aryl, C 7-13} arylalkylene, C _4-12 heterocycloalkyl, and C _3-12 heteroaryl, but not exceeding the normal valence of the substituted atom. The number of carbon atoms indicated in a group excludes any optional substituents. For example, --CH ₂ CH ₂ CN is a C ₂ alkyl group substituted with a nitrile.

While particular embodiments have been described, alternatives, variations, modifications, improvements, and substantial equivalents may occur to applicant or those skilled in the art that are not presently foreseen or possible. Accordingly, the appended claims, as filed and as they may be amended, are intended to embrace all such alternatives, variations, modifications, improvements, and substantial equivalents.

Claims (15)

5 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a first poly(phenylene ether);
1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene;
5 to 20 weight percent organophosphate flame retardant;
less than 3 weight percent reinforcing filler;
less than 0.5 weight percent tricalcium phosphate; and 40 to 90 weight percent of a second poly(phenylene ether),
A composition wherein the weight percentage of each component is based on the total weight of the composition. The composition of claim 1, wherein the second poly(phenylene ether) is present in an amount of 45 to 85 weight percent based on the total weight of the composition. The composition of claim 1 or 2, wherein the poly(phenylene ether)-poly(siloxane) block copolymer reaction product and the second poly(phenylene ether) are present in a combined amount of at least 70 weight percent, or from 70 to 94 weight percent, or from 75 to 85 weight percent, based on the total weight of the composition. 4. The composition according to claim 1, wherein a molded sample of the composition comprises:
UL-94 flammability rating of V0 when measured using 1.0 millimeter test specimens after conditioning at 23°C for 48 hours and at 70°C for 168 hours;
UL-94 flammability rating of V0 when measured using 0.75 millimeter test specimens after conditioning for 48 hours at 23°C and 168 hours at 70°C;
UL-94 flammability rating of V0 when measured using 0.5 millimeter test specimens after conditioning at 23°C for 48 hours and at 70°C for 168 hours;
UL-94 flammability rating of V0 when measured using 0.3 millimeter test specimens after conditioning at 23°C for 48 hours and at 70°C for 168 hours;
UL-94 flammability rating of V0 when measured using 0.2 millimeter test specimens after conditioning at 23° C. for 48 hours and at 70° C. for 168 hours; and
In some cases,
A composition characterized by exhibiting either or both of: a heat deflection temperature of 115°C or greater, as measured on 3.2 mm thick specimens using a load of 1.82 MPa according to ASTM D648; and a notched Izod impact strength of 240 J/m or greater, as measured according to ASTM D256. The composition according to any one of claims 1 to 4, wherein the first poly(phenylene ether) has an intrinsic viscosity greater than 0.25 deciliters per gram, or between 0.4 and 0.6 deciliters per gram, as measured in chloroform at 25°C using an Ubbelohde viscometer, and preferably the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether). The composition of any one of claims 1 to 5, characterized in that the organophosphate ester flame retardant comprises resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, resorcinol bis(di 2,6-dimethylphenyl) phosphate, oligomeric phosphate ester, triphenyl phosphate, or combinations thereof, preferably bis-phenol A bis-diphenyl phosphate. The composition according to any one of claims 1 to 6, characterized in that the hydrogenated block copolymer comprises polystyrene-poly(ethylene-butylene)-polystyrene. The composition according to any one of claims 1 to 7, characterized in that it contains 0 to 15 weight percent homopolystyrene or high impact polystyrene. A composition according to any one of claims 1 to 8, characterized in that it does not contain glass fibers. The composition according to any one of claims 1 to 9, further comprising 0.1 to 10 weight percent of an additive composition. 2. The composition of claim 1 ,
8 to 28 weight percent of said poly(phenylene ether)-polysiloxane block copolymer reaction product;
50 to 75 weight percent of said second poly(phenylene ether);
3 to 10 weight percent of said hydrogenated block copolymer; and 7 to 15 weight percent of said organophosphate flame retardant. The composition of claim 11, wherein the poly(phenylene ether)-poly(siloxane) block copolymer reaction product and the second poly(phenylene ether) are present in a combined amount of at least 75 weight percent, based on the total weight of the composition. A method for producing a composition according to any one or more of claims 1 to 12, comprising melt-mixing the components of the composition. An article comprising the composition of any one of claims 1 to 12,
Preferably, the article is an electric vehicle battery module, a battery insulating sheet or film, a battery housing, a battery case, a battery cell frame, a battery cell spacer, a battery cell retainer, a bus bar holder, a terminal cover, an electric or electronic component, a charger adapter insulating sheet or film, a thermosetting circuit breaker, a fuser holder for an electrophotographic copier, a photovoltaic junction box, a photovoltaic connector, an electrical connector, an automotive electrical connector, a relay, a charging coupler, an appliance part, an automotive part, a portable device, a mobile part, or a stationary electrical part. An electric vehicle battery part extruded from the composition of any one of claims 1 to 12, preferably an electric vehicle battery insulating sheet or film.